CN102910646B - Gradient acid distributed ZSM-5 molecular sieve and preparation method thereof - Google Patents
Gradient acid distributed ZSM-5 molecular sieve and preparation method thereof Download PDFInfo
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- CN102910646B CN102910646B CN201110217559.6A CN201110217559A CN102910646B CN 102910646 B CN102910646 B CN 102910646B CN 201110217559 A CN201110217559 A CN 201110217559A CN 102910646 B CN102910646 B CN 102910646B
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Abstract
The invention discloses a preparation method of a gradient acid distributed ZSM-5 molecular sieve. The ZSM-5 molecular sieve prepared by the method has a molar ratio of silicon oxide to alumina being 25-200, and simultaneously has weak acid, strong acid and super acid. The ZSM-5 molecular sieve having gradient acid distribution is obtained by supplementing an aluminium source to the ZSM-5 molecular sieve for a secondary synthesis. The ZSM-5 molecular sieve product obtained by the method has gradient acid properties, and has wide application prospects in the field of isomerization, alkylation, catalytic cracking and the like.
Description
Technical field
The invention belongs to Zeolite synthesis field, specifically relate to a kind of ZSM-5 molecular sieve with gradient acid distribution and preparation method thereof.
Background technology
Artificial synthetic zeolite's molecular sieve starts from 1948, with the zeolitization scholar headed by Barrer, successfully imitate the build environment of natural zeolite, the zeolite molecular sieve that synthesizes first batch of low silica-alumina ratio under hydrothermal condition is the basis that in big strides development established science of molecular sieve industry with science.Molecular sieve says it is by silica [SiO from its skeleton structure
4] and alumina [AlO
4] tetrahedron is that basic structural unit is shared Sauerstoffatom and formed, these [TO
4] tetrahedron is staggered to space reticulated structure, has more spacious skeleton structure and larger specific surface area, regular and uniform pore passage structure.
The skeleton structure of molecular sieve has determined its absorption, diffusion and the non-proton acid catalyzed performances such as shaped reaction of selecting; The chemical constitution of molecular sieve has determined the performances such as its acidity, thermostability; Both combinations, have determined the application performances such as its selection absorption, ion-exchange, sour shape selective catalysis and heat and hydrothermal stability.The synthetic of molecular sieve is the focus of molecular sieve research always.ZSM-5 is a kind of molecular sieve of the MFI of having topological framework, has the two-dimentional pore passage structure of " Z " font, and its silica alumina ratio can be from 25 to total silicon.ZSM-5 molecular sieve has good shape selective catalysis performance, is widely used in the catalytic fields such as alkylation, isomerization.
Current, very ripe and perfect about the synthetic method of ZSM-5 molecular sieve, comprise that silica alumina ratio is from 25 to infinite, from by template to without template agent method and the disclosed directing agent method of patent CN1303816A etc.The acidity of ZSM-5 molecular sieve, thermostability with and the singularity of pore passage structure, be therefore widely used in the catalytic fields such as alkylation, isomerization.
At present, the silica/alumina molar ratio of industrial ZSM-5 molecular sieve is 25-total silicon.The Acidity of ZSM-5 molecular sieve mainly comprises the weak acid between 100 ~ 300 ℃, the strong acid (NH between 350 ~ 450 ℃
3-TPD method is measured, i.e. NH
3the molecular sieve acid amount of the differing temps section that absorption programmed temperature method is measured).Total acid content is at 0.05 ~ 0.45mmol/g, and wherein Br nsted acid is lower than the molar ratio of Lewis acid.Strong acid and above acid amount are lower with the molar ratio of weak acid acid amount.For some, need the reaction process of super acids or the reaction process that super acids coordinates with strong acid and weak acid, the Acidity of ZSM-5 molecular sieve prepared by prior art cannot meet its demand, and its good Shape-selective cannot be applied.
Summary of the invention
For above-mentioned preparation method's shortcoming, the invention provides a kind of ZSM-5 molecular sieve and synthetic method thereof with gradient Acidity.It is acid that ZSM-5 molecular sieve of the present invention possesses weak acid acidity, strong acid acidity and super acids simultaneously, and particularly the quantity of super acids obviously exceeds the ZSM-5 molecular sieve that existing method obtains.
Gradient acid distribution ZSM-5 molecular sieve of the present invention has following character: the silica/alumina molar ratio of ZSM-5 molecular sieve is 25-100, possess simultaneously weak acid, strong acid with and super acids, total acid content is at 0.25 ~ 0.82mmol/g, wherein Br nsted acid than the mol ratio of Lewis acid between 1.1 ~ 2.1, be preferably 1.3～1.6, the mol ratio of strong acid acid amount and super acids acid amount sum and weak acid acid amount, between 1.2 ~ 2.0, is preferably 1.3～1.9.
The preparation method of gradient acid distribution ZSM-5 molecular sieve of the present invention comprises following content:
The first step, carries out crystallization by the mixture that contains sodium hydroxide, 4-propyl bromide or TPAOH, water, He Gui source, aluminium source;
Second step is added appropriate aluminium source in the mixture after the first step crystallization, and then crystallization is at a certain temperature washed, is dried, roasting crystallization product obtains gradient acid ZSM-5 molecular sieve.
In the inventive method, the first step synthesis material adds suitable material according to the conventional knowledge in this area, and it is Al that sodium hydroxide, 4-propyl bromide or TPAOH, water, He Gui source, aluminium source composition mixture be take the mol ratio of following material
2o
3: 20-250SiO
2: 10-30 TPA
+: 8-15Na
2o:3600-6000H
2o.TPA wherein
+for tetrapropyl radical ion.Crystallization condition is at 120 ℃ ~ 200 ℃, crystallization 12h ~ 72h.In second step, the crystallization temperature of mixture is at 120 ℃ ~ 200 ℃, crystallization 12h ~ 72h.
In the inventive method, the silicon source described in the first step is silicon sol or white carbon black.Aluminium source described in the first step is sodium aluminate, Tai-Ace S 150 or aluminum nitrate; Aluminium source described in second step is Tai-Ace S 150 or aluminum nitrate.The aluminium source adding in second step is the 10%-200% of the aluminium source amount described in the first step, is preferably 50%-100%(mass percent, with Al
2o
3meter).
In molecular sieve preparation method of the present invention, after the first step crystallization, can carry out cooling being depressurized to and can open crystallization equipment, then add aluminium source, carry out second step crystallization; Also can adopt suitable feeding equipment, the required aluminium source of second step is directly added in the first step crystallization equipment, under agitation condition, carry out second step crystallization.
The inventive method is by the selection of suitable template, silicon source and aluminium source category, and suitable building-up process, has obtained having the ZSM-5 molecular sieve of gradient acid distribution property.This molecular sieve has the Gradient distribution of weak acid-strong acid-super acids, for needing the catalytic process of the more catalytic reaction process of strong acid amount or needs acid amount Gradient distribution that good catalytic material is provided.The ZSM-5 molecular sieve with gradient acid distribution property that the present invention synthesizes has outstanding reaction effect at catalytic fields such as alkylation, isomerization.
Accompanying drawing explanation
Fig. 1 is the XRD diffractogram of the embodiment of the present invention 1 sintetics.
Fig. 2 is the acid distribution spectrogram of the embodiment of the present invention 1 sintetics.
Fig. 3 is the acid distribution spectrogram of the ZSM-5 molecular sieve of ordinary method synthetic [see Catalysis Today 93-95(2004) 729-734].
Embodiment
Below in conjunction with embodiment, further illustrate preparation process of the present invention.
Embodiment 1
The first step, 1.6g sodium hydroxide and 1.2g Tai-Ace S 150 are joined respectively in 140ml deionized water, taking 4-propyl bromide 7.5g joins in solution, after stirring half an hour, add 15ml silicon sol, after stirring, pack in stainless steel crystallizing kettle, 180 ℃ of thermostatic crystallizations 12 hours, are then cooled to room temperature.
Synthesis material proportioning: Al
2o
3: 50SiO
2: 15.6 TPA
+: 11.1Na
2o:4700H
2o
Second step, stirs mixture cooling after crystallization, directly adds 1.2g Tai-Ace S 150 after stirring, then stir after 2.0h, pack in stainless steel crystallizing kettle, 180 ℃ of thermostatic crystallizations 18 hours, then be cooled to room temperature, washing, dry, roasting obtain ZSM-5 molecular sieve.
Embodiment 2
The first step, 1.8g sodium hydroxide and 1.2g Tai-Ace S 150 are joined respectively in 120ml deionized water, taking 4-propyl bromide 7.5g joins in solution, after stirring half an hour, add 20ml silicon sol, after stirring, pack in stainless steel crystallizing kettle, 180 ℃ of thermostatic crystallizations 18 hours, are then cooled to room temperature.
Synthesis material proportioning: Al
2o
3: 67SiO
2: 15.6 TPA
+: 12.5Na
2o:4222H
2o
Second step, stirs mixture cooling after crystallization, directly adds 0.5g aluminum nitrate after stirring, then stir after 2.0h, pack in stainless steel crystallizing kettle, 140 ℃ of thermostatic crystallizations 24 hours, then be cooled to room temperature, washing, dry, roasting obtain ZSM-5 molecular sieve.
Embodiment 3
The first step, 1.6g sodium hydroxide and 1.2g Tai-Ace S 150 are joined respectively in 150ml deionized water, taking 4-propyl bromide 10g joins in solution, after stirring half an hour, add 25ml silicon sol, after stirring, pack in stainless steel crystallizing kettle, 140 ℃ of thermostatic crystallizations 48 hours, are then cooled to room temperature.
Synthesis material proportioning: Al
2o
3: 83SiO
2: 20.8 TPA
+: 11.1Na
2o:5277H
2o
Second step, stirs mixture cooling after crystallization, directly adds 1.2g Tai-Ace S 150 after stirring, then stir after 2.0h, pack in stainless steel crystallizing kettle, 180 ℃ of thermostatic crystallizations 18 hours, then be cooled to room temperature, washing, dry, roasting obtain ZSM-5 molecular sieve.
Embodiment 4
The first step, 1.6g sodium hydroxide and 1.2g Tai-Ace S 150 are joined respectively in 150ml deionized water, taking 4-propyl bromide 7.5g joins in solution, after stirring half an hour, add 30ml silicon sol, after stirring, pack in stainless steel crystallizing kettle, 170 ℃ of thermostatic crystallizations 48 hours, are then cooled to room temperature.
Synthesis material proportioning: Al
2o
3: 100SiO
2: 15.6 TPA
+: 11.1Na
2o:5407H
2o
Second step, stirs mixture cooling after crystallization, directly adds 2.5g Tai-Ace S 150 after stirring, then stir after 2.0h, pack in stainless steel crystallizing kettle, 180 ℃ of thermostatic crystallizations 24 hours, then be cooled to room temperature, washing, dry, roasting obtain ZSM-5 molecular sieve.
Embodiment 5
The first step, 1.5g sodium hydroxide and 0.42g sodium aluminate are joined respectively in 140ml deionized water, taking 4-propyl bromide 7.5g joins in solution, after stirring half an hour, add 15ml silicon sol, after stirring, pack in stainless steel crystallizing kettle, 180 ℃ of thermostatic crystallizations 12 hours, are then cooled to room temperature.
Synthesis material proportioning: Al
2o
3: 50SiO
2: 15.6 TPA
+: 11.1Na
2o:4700H
2o
Second step, stirs mixture cooling after crystallization, directly adds 1.2g Tai-Ace S 150 after stirring, then stir after 2.0h, pack in stainless steel crystallizing kettle, 180 ℃ of thermostatic crystallizations 18 hours, then be cooled to room temperature, washing, dry, roasting obtain ZSM-5 molecular sieve.
Comparative example
By existing method, 1.5g sodium hydroxide and 0.42g sodium aluminate are joined respectively in 140ml deionized water, taking 4-propyl bromide 7.5g joins in solution, after stirring half an hour, add 15ml silicon sol, after stirring, pack in stainless steel crystallizing kettle 180 ℃ of thermostatic crystallizations 24 hours into, then be cooled to room temperature, washing, dry, roasting obtain ZSM-5 molecular sieve.
Synthesis material proportioning: Al
2o
3: 50SiO
2: 15.6 TPA
+: 11.1Na
2o:4700H
2o.
Table 1 zeolite product parameter.
| Sample | SiO 2/Al 2O 3(mol ratio) | Total acid content (mmol/g) | Br nsted/Lewis(mol ratio) | The mol ratio of strong acid and super acids acid amount sum and weak acid acid amount |
| Comparative example | 45 | 0.633 | 1.05 | 1.02 |
| Example 1 | 38 | 0.651 | 1.51 | 1.35 |
| Example 2 | 49 | 0.602 | 1.42 | 1.38 |
| Example 3 | 58 | 0.522 | 1.35 | 1.54 |
| Example 4 | 86 | 0.302 | 1.30 | 1.62 |
| Example 5 | 40 | 0.644 | 1.49 | 1.80 |
The sign of gradient acid distribution ZSM-5 molecular sieve:
Molecular sieve ammonium exchange: the molecular sieve of roasting removed template method and 0.5-2.0mol/L ammonium nitrate solution are exchanged 2 times under 50-100 ℃ of water bath condition, be 1-5h each swap time, distilled water wash is removed nitrate ion, and 120 ℃ obtain Hydrogen ZSM-5 molecular sieve after dry after 350-650 ℃ of roasting 4h.
In gradient acid distribution ZSM-5 molecular sieve of the present invention, gradient acid distributes and refers to have weak acid, strong acid and super acids in ZSM-5 molecular sieve simultaneously, and weak acid strength of acid is wherein NH
3acid between 100 ~ 300 ℃ of the analysis of-TPD method, strong acid strength of acid is NH
3acid between 350 ~ 450 ℃ of the analysis of-TPD method, super acids strength of acid is NH
3acid between 450 ~ 650 ℃ of the analysis of-TPD method.Br nsted acid (being B acid) and acid amount and Lewis acid (being L acid) and sour quantitative analysis method are pyridine-infrared (Py-IR) sour measuring method.
NH
3-TPD analyzes: on Micromeritics 2910 instruments that experiment is produced in U.S. Merck & Co., Inc, test.Before experiment, sample need be processed 2h at 650 ℃, is down to 100 ℃ of constant temperature and starts logical NH
3keep 0.5h, then use nitrogen purging until baseline balance.Temperature program(me) is warmed up to 650 ℃, obtains the NH of molecular sieve
3-TPD desorption figure (accompanying drawing 2).On the 560 type infrared spectrophotometers that the analysis of Br nsted acid and Lewis acid is produced in U.S. Buddhist nun's high-tensile strength company, carry out.Concrete grammar is as follows: sample is purified to 4h under 500 ℃, 60mPa in reaction tubes, drop to room temperature and be evacuated to 0.1mPa Adsorption of Pyridine.Then be warming up to respectively 160 ℃ of pyridines that remove physical adsorption.The pyridine of 160 ℃ and above desorption is as the total acid content of catalyzer, and on IR instrument, measures B acid and L acid (mensuration at 160 ℃).
Claims (8)
1. a preparation method for gradient acid distribution ZSM-5 molecular sieve, is characterized in that comprising following content:
The first step, carries out crystallization by the mixture that contains sodium hydroxide, 4-propyl bromide or TPAOH, water, He Gui source, aluminium source;
Second step is added aluminium source in the mixture after the first step crystallization, and then crystallization at 120 ℃～200 ℃ is washed, is dried, roasting crystallization product obtains gradient acid ZSM-5 molecular sieve; The aluminium source wherein adding in second step is the 10%-200% of the aluminium source amount described in the first step, with Al
2o
3mass percent meter; Described gradient acid ZSM-5 molecular sieve has following character: the silica/alumina molar ratio of ZSM-5 molecular sieve is 25-100, possesses weak acid, strong acid and super acids simultaneously, and total acid content is at 0.25～0.82mmol/g, wherein
acid is than the mol ratio of Lewis acid between 1.1～2.1, and the mol ratio of strong acid acid amount and super acids acid amount sum and weak acid acid amount is between 1.2～2.0.
2. in accordance with the method for claim 1, it is characterized in that: in the first step synthesis material, it is Al that sodium hydroxide, 4-propyl bromide or TPAOH, water, He Gui source, aluminium source composition mixture be take the mol ratio of following material
2o
3: 20-250SiO
2: 10-30TPA
+: 8-15Na
2o:3600-6000H
2o, wherein TPA
+for tetrapropyl radical ion.
3. in accordance with the method for claim 1, it is characterized in that: the crystallization condition of the first step is at 120 ℃～200 ℃, crystallization 12h～72h; In second step, the crystallization condition of mixture is at 120 ℃～200 ℃, crystallization 12h～72h.
4. it is characterized in that in accordance with the method for claim 1: the silicon source described in the first step is silicon sol or white carbon black.
5. it is characterized in that in accordance with the method for claim 1: the aluminium source described in the first step is sodium aluminate, Tai-Ace S 150 or aluminum nitrate; Aluminium source described in second step is Tai-Ace S 150 or aluminum nitrate.
6. according to the method described in claim 1 or 5, it is characterized in that: the aluminium source adding in second step is the 50%-100% of the aluminium source amount described in the first step, with Al
2o
3mass percent meter.
7. it is characterized in that in accordance with the method for claim 1: gradient acid ZSM-5 molecular sieve
acid is 1.3～1.6 than the mol ratio of Lewis acid.
8. according to the method described in claim 1 or 7, it is characterized in that: the mol ratio of the strong acid acid amount of gradient acid ZSM-5 molecular sieve and super acids acid amount sum and weak acid acid amount is 1.3～1.9.
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|---|---|---|---|---|
| CN103880037B (en) * | 2012-12-20 | 2015-07-22 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve and preparation method thereof |
| CN103880038B (en) * | 2012-12-20 | 2015-07-22 | 中国石油化工股份有限公司 | ZSM-5 molecular sieve with different acid distribution and preparation method thereof |
| CN105712378B (en) * | 2014-12-02 | 2018-10-09 | 中国科学院大连化学物理研究所 | A kind of synthetic method of nano-ZSM-5 molecular sieve |
| CN107226474A (en) * | 2016-03-23 | 2017-10-03 | 中国石化扬子石油化工有限公司 | Mend aluminium method of modifying in a kind of ZSM-5 original positions |
| CN107840350B (en) * | 2016-09-19 | 2020-08-07 | 中国石油化工股份有限公司 | Synthesis method of nano ZSM-5 molecular sieve with controllable particle size distribution |
| MY192332A (en) * | 2016-10-03 | 2022-08-17 | Basf Corp | Aluminum gradient aluminosilicate zeolite compositions |
| CN108178163B (en) * | 2017-12-27 | 2019-11-26 | 中国石油大学(北京) | A kind of low silicon multilevel structure ZSM-5 zeolite molecular sieve and its preparation method and application |
| CN111217379B (en) * | 2018-11-26 | 2022-12-06 | 中国石油天然气股份有限公司 | Method for synthesizing MTW type molecular sieve with low silicon-aluminum ratio |
| CN111252783A (en) * | 2018-11-30 | 2020-06-09 | 中国科学院大连化学物理研究所 | Low silicon-aluminum ratio MFI type molecular sieve synthesis method |
| CN111252782B (en) * | 2018-11-30 | 2022-09-23 | 中国科学院大连化学物理研究所 | Synthetic method of Beta molecular sieve with low silicon-aluminum ratio |
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